Binary alloys based on polyether-amides and cycloolefin polymers

ABSTRACT

Polymer alloys based on (a) at least one thermoplastic, aromatic polyether-amide having a molecular weight of from 5000 to 40,000 and (b) at least one cycloolefin polymer are prepared. The proportions of the components are 99-50% by weight of (a) and 1-50% by weight of (b), the proportions adding up to 100% by weight, based on the total alloy. The polymer alloys can be used for the production of moldings.

DESCRIPTION

Both amorphous and partially crystalline aromatic polyether-amides whichcan be processed as thermoplastics can be prepared in various molecularweights. These thermoplastic aromatic polyether-amides have beendescribed in a German Patent Application (P 40 38 393) which has anearlier priority date, but was not published before the date ofapplication of the present application; express reference is made tothis patent application. These aromatic polyether-amides are a valuableclass of polymers which has a high level of properties and isdistinguished, inter alia, by good solvent resistance.

However, for some applications, for example as matrix materials forcomposites, it is desirable for these polyether-amides to have lowermelt viscosities and lower water-absorption capacities.

It is known that technologically important properties of polymers, suchas melt viscosity and water-absorption capacity, can be adjusted byalloying polymers with other polymers. However, reliable prediction ofthe properties of an alloy from the properties of the individualcomponents is hitherto still distant. Alloying of polymers thereforeremains substantially empirical.

DD-A-203 060 discloses alloys of norbornene-ethylene copolymers andpolyamides. Polyamides which can be employed are, in particular,aliphatic polyamides, such as nylon 6 and nylon 6,6, and polyamidescontaining cycloaliphatic or aromatic chain members. The only example ofa fully aromatic polyamide mentioned is poly-m-phenylene isophthalamide,but this cannot be processed by standard techniques for processingthermoplastics, such as extrusion or injection molding.

The object of the invention is therefore to provide alloys ofthermoplastic aromatic polyether-amides with other polymers, whichalloys have lower melt viscosities and lower water-absorption capacitiesthan do the polyether-amides alone.

The invention relates to polymer alloys containing at least twocomponents (a) and (b), wherein (a) is at least one thermoplasticaromatic polyether-amide of the formula (I) ##STR1## in which thesymbols --Ar--, --Ar'--, --Ar₁ --, --Ar₂ --, --R--, --R'--, --Y--, x, yand z are as defined below:

--Ar-- is a divalent, substituted or unsubstituted, aromatic orheteroaromatic radical or an --Ar*--Q--Ar*-- group,

in which --Q-- is a bond or an --O--, --CO--, --S--, --SO-- or --SO₂--bridge, and --Ar*-- is an aromatic radical,

--Ar'-- is as defined for --Ar-- or is an --Ar--Z--Ar-- group where--Z-- is a --C(CH₃)₂ -- or --O--Ar*--O-- bridge,

--Ar₁ -- and --Ar₂ -- are identical or different and are each asubstituted or unsubstituted para- or meta-arylene radical, for examplemeta- or para-phenylene,

--Y-- is a --C(CH₃)₂ --, --SO₂ --, --S-- or --C(CF₃)₂ -- bridge, itbeing possible for up to two different radicals Y to be bonded in thesame polymer,

the sum of the molar fractions x, y and z is one, the sum of x and z isnot equal to y, and x can adopt the value zero,

the ends of the polymer chain are fully blocked by monofunctional groups--R and --R' which do not react further in the polymer, where --R and--R', independently of one another, are identical or different, and

the polyether-amide has a mean molecular weight in the range from 5000to 40,000, and

(b) is at least one cycloolefin polymer, where the proportion of (a) is99-50% by weight, and the proportion of (b) is 1-50% by weight, based onthe sum of the proportions of (a) and (b). It is preferred to employ 1or 2 components (a).

It is preferred for the proportion of component (a) to be 98-60% byweight, in particular 95-85% by weight, and that of component (b) to be2-40% by weight, in particular 5-15% by weight, based on the sum ofcomponents (a) and (b).

In component (a), z is preferably greater than x. The molecular weightis adjusted during the preparation of a) by adding the monomer units innon-stoichiometric amounts. The polyether-amides (a) are prepared bypolycondensation. When the polycondensation reaction is complete, theends of the polymer chains are fully blocked by adding at leaststoichiometric amounts of monofunctional reagents which react in thepolymer to form groups R and R' which do not react further. The terminalgroups R and R' are independent of one another and are identical ordifferent, preferably identical. The terminal groups --R and --R' arepreferably selected from the group comprising the radicals of theformulae II, III, IV and/or V ##STR2##

In the terminal groups IV and V, the terminal nitrogen in the formula Iis in the form of an imide nitrogen (and not of NH); in the terminalgroups II and III, the terminal nitrogen is in the form of an amide. Inthe abovementioned formulae, E is a hydrogen or halogen atom, inparticular a chlorine, bromine or fluorine atom, or an organic radical,for example an aryl(oxy) group, such as phenoxy, or a C₁ -C₃ -alkyl orC₁ -C₃ -alkoxy group.

In the preparation of the polyether-amide (a) by reacting one or moredicarboxylic acid derivatives with one or more diamines by the solutionor melt condensation process, one of the components is employed in lessthan the stoichiometric amount, and a chain terminator is added when thepolycondensation is complete. It is preferred to employ up to threedifferent dicarboxylic acid derivatives VI and up to three diamines VIIand VIII for the preparation of the polyether-amides used.

The polyether-amides employed are preferably prepared by solutioncondensation.

The solution condensation of the aromatic dicarboxylic dichloride withthe aromatic diamines is carried out in an aprotic, polar solvent of theamide type, for example N,N-dimethylacetamide, preferablyN-methyl-2-pyrrolidone. If desired, halide salts of metals from thefirst and/or second group of the Periodic Table of the Elements areadded to the solvent in a known manner in order to increase the solvencyor to stabilize the polyether-amide solutions. Preferred additives arecalcium chloride and/or lithium chloride. The condensation is preferablycarried out without adding salt, since the above-described aromaticpolyamides are distinguished by high solubility in the abovementionedsolvents of the amide type.

In this way, fusible polyether-amides having good mechanical properties,in particular high initial modulus, good tear strength and gooddielectric strength, and which allow processing by standard methods forprocessing thermoplastics, can be prepared if at least one of thestarting components is employed in less than the stoichiometric amount.In this way, it is possible to limit the molecular weight in accordancewith the known Carothers equation: ##EQU1## where q is not equal to 1and simultaneously ##EQU2## p_(n) is the degree of polymerization and qis the molar ratio between the diacid component and the amine component.

If less than the stoichiometric amount of acid dichloride is used, thechain terminator added at the end of the polymerization reaction is amonofunctional, aromatic acid chloride or acid anhydride, for examplebenzoyl chloride, fluorobenzoyl chloride, diphenylcarbonyl chloride,phenoxybenzoyl chloride, phthalic anhydride, naphthalic anhydride or4-chloronaphthalic anhydride.

If desired, chain terminators of this type may be substituted,preferably by fluorine or chlorine atoms. Preference is given to benzoylchloride or phthalic anhydride, in particular benzoyl chloride.

If less than the stoichiometric amount of the diamine component is used,the chain terminator added at the end of the polycondensation is amonofunctional, preferably aromatic amine, for example fluoroaniline,chloroaniline, 4-aminodiphenylamine, aminobiphenylamine, aminodiphenylether, aminobenzophenone or aminoquinoline.

The polycondensation is preferably carried out by polycondensing thediacid chloride in less than the stoichiometric amount with the diamine,and the reactive amino groups remaining are subsequently deactivated bymeans of a monofunctional acid chloride or diacid anhydride.

In a further preferred embodiment, the diacid chloride is employed inless than the stoichiometric amount and polycondensed with a diamine.The reactive amino terminal groups which remain are subsequentlydeactivated by means of a monofunctional, preferably aromatic,substituted or unsubstituted acid chloride or acid anhydride.

The chain terminator, the monofunctional amine or acid chloride or acidanhydride, is preferably employed in a stoichiometric orsuperstoichiometric amount, based on the diacid or diamine components.

The two carbonyl groups attached to the divalent radical Ar arepreferably not on adjacent ring carbon atoms (example: phthalic acid).If they are on the same aromatic ring of the radical Ar, the para- ormeta-position is preferred. They may also be attached to different rings(example: 2,6-naphthalenedicarboxylic acid). The divalent radical Ar mayalso be substituted, in particular by one or two branched or unbranchedC₁ -C₃ -alkyl or alkoxy radicals, aryl or aryloxy radicals, such asphenyl and phenoxy, C₁ -C₆ -perfluoroalkyl or perfluoroalkoxy radicals,or by fluorine, chlorine, bromine or iodine atoms. The same applies tothe divalent radicals Ar₁, Ar₂, Ar' and Ar*.

The polyether-amide (a) may simultaneously contain up to three differentradicals Ar.

The aromatic radicals, in particular the divalent radicals Ar, Ar', Ar₁,Ar₂ and Ar*, comprise 1 or 2 isocyclic aromatic rings, such as, forexample, naphthalene. Phenylene radicals are preferred. Theheteroaromatic radicals Ar and Ar' are derived from a heterocyclicaromatic ring, in particular furan, thiophene, pyridine or aheterocyclic compound comprising 2 fused rings, for exampleisoquinoline.

Aromatic polyether-amides (a) are prepared by reacting one or moredicarboxylic acid derivatives with one or more diamines by knownsolution, precipitation or melt condensation processes (P. W. Morgan,Condensation Polymers by Interfacial and Solution methods, IntersciencePublishers 1965, and Vollbracht, Aromatic Polyamides, ComprehensivePolymer Sci., Vol. 5, p. 375 (1989)), one of the components beingemployed in less than the stoichiometric amount, and a chain terminatorbeing added when the polycondensation is complete.

Particularly suitable dicarboxylic acid derivatives for the preparationof the polyether-amides (a) are those of the formula VI

    W--CO--Ar--CO--W                                           (VI)

where --Ar-- is as defined above, and --W is a fluorine, chlorine,bromine or iodine atom, preferably a chlorine atom, or an --OH or --OR"group, and R" is a branched or unbranched, aliphatic or aromaticradical.

Examples of compounds of the formula VI are:

terephthalic acid

terephthaloyl dichloride

diphenyl terephthalate

isophthalic acid

diphenyl iosphthalate

isophthaloyl chloride

phenoxyterephthalic acid

phenoxyterephthaloyl dichloride

diphenyl phenoxyterephthalate

di(n-hexyloxy)terephthalic acid

bis(n-hexyloxy)terephthaloyl dichloride

diphenyl bis(n-hexyloxy)terephthalate

2,5-furandicarboxylic acid

2,5-furandicarbonyl chloride

diphenyl 2,5-furandicarboxylate

thiophenedicarboxylic acid

naphthalene-2,6-dicarboxylic acid

diphenyl ether 4,4'-dicarboxylic acid

benzophenone-4,4'-dicarboxylic acid

isopropylidene-4,4'-dibenzoic acid

diphenyl sulfone 4,4'-dicarboxylic acid

tetraphenylthiophenedicarboxylic acid

diphenyl sulfoxide-4,4'-dicarboxylic acid

diphenyl thioether 4,4'-dicarboxylic acid and

trimethylphenylindanedicarboxylic acid.

The dicarboxylic acid derivatives of the formula VI are reacted witharomatic diamines, for example of the formula VII

    H.sub.2 N--Ar'--NH.sub.2                                   (VII)

in which Ar'-- is as defined above. The following compounds arepreferably suitable for this reaction:

m-phenylenediamine

p-phenylenediamine

2,4-dichloro-p-phenylenediamine

diaminopyridine

1,2-, 1,3- and 1,4-bis(3- and 4-aminophenoxy)benzene

2,6-bis(aminophenoxy)pyridine

3,3'-dimethylbenzidene

4,4'- and 3,4'-diaminodiphenyl ether

isopropylidene-4,4'-dianiline

p,p'- and m,m'-bis(4-aminophenylisopropylidene)benzene

4,4'- and 3,3'-diaminobenzophenone

4,4'- and 3,3'-diaminodiphenyl sulfone and

bis(2-amino-3-methylbenzo)thiophene S,S-dioxide.

Other aromatic diamines which can be employed are those of the formulaVIII

    H.sub.2 N--Ar.sub.1 --O--Ar.sub.2 --Y--Ar.sub.2 --O--Ar.sub.1 --NH.sub.2 (VIII)

where Ar₁, Ar₂ and Y are as defined above. Particularly suitablearomatic diamines of the formula VIII are the following:

2,2-bis[4-(3-trifluoromethyl-4-aminophenoxy)phenyl]propane,

bis[4-(4-aminophenoxy)phenyl]sulfide,

bis[4-(3-aminophenoxy)phenyl]sulfide,

bis[4-(3-aminophenoxy)phenyl]sulfone,

bis[4-(4-aminophenoxy)phenyl]sulfone,

2,2-bis[4-(4-aminophenoxy)phenyl]propane,

2,2-bis[4-(3-aminophenoxy)phenyl]propane,

2,2-bis[4-(2-aminophenoxy)phenyl]propane and

1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane.

These amines are known to persons skilled in the art or can be obtainedin a simple manner by known methods. For example,1,4-bis(p-chlorophenoxy)benzene (═"BCB") is obtained fromp-dichlorobenzene and p-chlorophenol. BCB+p-aminothiophenol gives (NH₂C₆ H₄ --S--C₆ H₄ O)₂ C₆ H₄, a diamine containing 5 aromatic rings.

The molar ratio (MR) between the acid component and the diaminecomponent can be varied in the range from 0.90 to 1.10, exactstoichiometry (MR=1.00) of the bifunctional components being excluded,since otherwise the desired molecular weight can only be achieved withdifficulty.

The molar ratio MR is preferably in the range from 0.90 to 0.99 and from1.01 to 1.10, particularly preferably in the range from 0.93 to 0.98 andfrom 1.02 to 1.07, in particular in the range from 0.95 to 0.97 and from1.03 to 1.05.

The polycondensation temperature is usually in the range from -20° to+120° C., preferably from +10° to +100° C.

Particularly good results are achieved at reaction temperatures of from+10° to +80° C. The polycondensation reactions are preferably carriedout so that, when the reaction is complete, from 2 to 40% by weight,preferably from 5 to 30% by weight, of polycondensate is present in thesolution. For specific applications, the solution may, if required, bediluted with N-methyl-2-pyrrolidone or other solvents, for exampledimethylformamide, N,N-dimethylacetamide or butylcellosolve orconcentrated under reduced pressure (thin-film evaporator).

When the polycondensation is complete, the hydrogen chloride formed,which is loosely bonded to the amide solvent, is removed by addingacid-binding assistants, for example lithium hydroxide, calciumhydroxide, but in particular calcium oxide, propylene oxide, ethyleneoxide or ammonia. In a particular embodiment, the "acid-binding" agentused is pure water, which dilutes the hydrochloric acid andsimultaneously serves to precipitate the polymer.

In order to isolate the polyether-amide, a precipitant can be added tothe solution and the coagulated product filtered off. Examples oftypical precipitants are water, methanol and acetone, which may, ifdesired, also contain pH-controlling additives, such as, for example,ammonia or acetic acid.

The polyether-amide is preferably isolated by comminuting the polymersolution using an excess of water in a cutting mill. The finelycomminuted, coagulated polymer particles simplify the subsequent washingsteps (removal of the secondary products formed from the hydrogenchloride) and the drying of the polymer (avoidance of inclusions) afterfiltering off. Subsequent comminution is also superfluous since afree-flowing product is formed directly.

Apart from the solution condensation described, which is regarded asbeing a readily accessible process, it is also possible, as statedabove, to use other conventional processes for the preparation ofpolyamides, such as, for example, melt or solid condensation. Inaddition to the condensation with regulation of the molecular weight,these processes may also contain purification or washing steps and theaddition of suitable additives. The additives may, in addition, also beadded to the isolated polymer subsequently during thermoplasticprocessing.

The polyether-amides (a) have a Staudinger index η of from 0.4 to 1.5dl/g, preferably from 0.5 to 1.3 dl/g, particularly preferably from 0.6to 1.1 dl/g, measured at 25° C. in N-methyl-2-pyrrolidone.

Cycloolefin polymers (b) which are suitable for the alloys of theinvention contain structural units derived from at least one monomer ofthe formulae IX to XIV or XV ##STR3## in which R¹, R², R³, R⁴, R⁵, R⁶,R⁷ and R⁸ are identical or different and are hydrogen atoms or C₁ -C₈-alkyl radicals, it being possible for identical radicals in the variousformulae to have different meanings, and n is an integer from 2 to 10.

In addition to the structural units derived from at least one monomer ofthe formulae IX to XV, the cycloolefin polymers of the invention maycontain further structural units derived from at least one acyclic1-olefin of the formula XVI ##STR4## in which R⁹, R¹⁰, R¹¹ and R¹² areidentical or different and are hydrogen atoms or C₁ -C₈ -alkyl radicals.

Preferred comonomers of the formula XVI are ethylene and propylene. Inparticular, copolymers of polycyclic olefins of the formula IX or XI andthe acyclic olefins of the formula XVI, preferably of norbornene andethylene, are employed. Particularly preferred cycloolefins arenorbornene and tetracyclododecene, which may be substituted by C₁ -C₆-alkyl, ethylene-norbornene copolymers being of particular importance.Of the monocyclic olefins of the formula XV, cyclopentene, which may besubstituted, is preferred. Polycyclic olefins, monocyclic olefins andopen-chain olefins are also taken to mean mixtures of two or moreolefins of the particular type. This means that cycloolefin homopolymersand copolymers, such as bipolymers, terpolymers and multipolymers, canbe employed.

The cycloolefin polymerizations which proceed with opening of the doublebond can be catalyzed homogeneously, i.e. the catalyst system is solublein the polymerization medium (DE-A-3 922 546 and EP-A-0 203 799), or canbe catalyzed by means of a classical Ziegler catalyst system (DD-A-222317 and DD-A-239 409).

Cycloolefin homopolymers and copolymers which contain structural unitsderived from monomers of the formulae IX to XIV or XV are preferablyprepared with the aid of a homogeneous catalyst comprising a metallocenewhose central atom is a metal from the group comprising titanium,zirconium, hafnium, vanadium, niobium and tantalum and which forms asandwich structure together with two mutually bridged monocyclic orpolycyclic ligands, and an aluminoxane. The bridged metallocenes areprepared by a known reaction scheme (cf. J. Organomet. Chem. 288 (1985)63-67, and EP-A-320 762). The aluminoxane, which functions as acocatalyst, can be obtained by various methods (cf. S. Pasynkiewicz,Polyhedron 9 (1990) 429). The structure and synthesis of this catalystand the conditions which are suitable for the polymerization of thesecycloolefins are described in detail in DE-A-3 922 546 and in GermanPatent Application P 4 036 264.7. Preference is given to cycloolefinpolymers having a viscosity of greater than 20 cm³ /g, measured indecahydronaphthalene at 135° C., and a glass transition temperature offrom 100° to 200° C.

The alloys may also contain, as constituents (b), cycloolefin polymersobtained from cycloolefins with ring opening in the presence of, forexample, tungsten-, molybdenum-, rhodium- or rhenium-containingcatalysts. The cycloolefin polymers obtained have double bonds which canbe removed by hydrogenation (U.S. Pat. No. 3,557,072 and U.S. Pat. No.4,178,424).

The cycloolefin polymers employed for the alloys of the invention mayalso be modified by grafting with at least one monomer selected from thegroup comprising (1) α,β-unsaturated carboxylic acids and/or derivativesthereof, (2) styrenes, (3) organic silicone components containing anolefinic unsaturated bond and a hydrolyzable group and (4) unsaturatedepoxy components. The modified cycloolefin polymers obtained haveexcellent properties at a similar level to those of the unmodifiedcycloolefin polymers. In addition, they specifically have good adhesionto metals and synthetic polymers. The good compatibility with otherpolymers should be emphasized.

The alloys of the invention are prepared by known alloying methods. Forexample, the alloy partners are extruded jointly in an extruder in theform of powders or granules to give extrudates, and the extrudates aregranulated and converted into the desired shape, for example bycompression molding or injection molding.

The alloys may contain additives, for example thermal stabilizers, UVstabilizers, impact modifiers or reinforcing additives, such as glassfibers or carbon fibers.

The alloys may advantageously be employed for the production of moldingsby injection molding or extrusion, for example in the form of fibers,films, tubes or cable coverings.

The invention is described in greater detail by the examples.

The polymers below were synthesized and employed in the examples:

Polyether-amide I [PEA I] having a Staudinger index of 0.6 dl/g,measured in N-methyl-2-pyrrolidone at 25° C., and a molecular weightM_(n) (GPC) of 27,000 g/mol (relative to polystyrene) and containingrecurring units of the formula below: ##STR5## Preparation of PEA I

4105 g (10 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]-propane weredissolved in 15.24 l of N-methylpyrrolidone under nitrogen in anenameled 40 l stirred reactor with heating jacket. After the temperaturehad equilibrated at 25° C., 1959 g (9.65 mol=96.5%) of terephthaloylchloride, dissolved in 5 l of N-methylpyrrolidone, were added. 30minutes after the mixture had reached 70° C., 112.5 g (0.8 mol) ofbenzoyl chloride were added, after a further 30 minutes the mixture wascooled to 60° C., and 566 g (10.1 mol) of CaO as a suspension in 305 gof N-methylpyrrolidone were added. After 1 hour, the clear, viscoussolution was discharged from the reactor, diluted from a polymer contentof 20% to about 13% by means of about 13 l of N-methylpyrrolidone, andfiltered under an N₂ pressure of 3 bar, and finally the polymer wasprecipitated as a fine powder (particle size≦1 mm) using water. Thepolymer powder was washed four times for 2 hours in each case with 60 lof fresh, demineralized water at 95°-98° C. in a stirred pressurefilter, dried roughly in a hot stream of nitrogen and washed a furthertwice with 60 l of acetone (2 hours, 60° C.). The product was predriedovernight in a stream of nitrogen, subsequently dried for 14 hours at130° C. (100 mbar) and finally dried to completion for 8 hours at 150°C. (<10 mbar). Yield 5.0 kg (93%).

Polyether-amide II [PEA II] having a Staudinger index of 0.6 dl/g,measured in N-methyl-2-pyrrolidone at 25° C., and a molecular weightM_(n) (GPC) of 27,000 g/mol (relative to polystyrene), and containingstructural units q and r of the formulae: ##STR6## where the proportionof q is 80 mol % and the proportion of r is 20 mol %. Preparation of PEAII

4105 g (10 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]-propane werereacted analogously to the preparation of PEA I with 1949 g (9.6 mol) ofterephthaloyl and isophthaloyl chloride in the ratio 8:2 and with 126.5g (0.9 mol) of benzoyl chloride in 20.8 kg of N-methyl-2-pyrrolidone.

Cycloolefin copolymer I (COC I)

A) Preparation ofdiphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride

A solution of 5.10 g (30.7 mmol) of fluorene in 60 cm³ of THF wastreated slowly at room temperature with 12.3 cm³ (30.7 mmol) of a 2.5molar hexane solution of n-butyllithium. After 40 minutes, 7.07 g (30.7mmol) of diphenylfulvene were added to the orange solution, and themixture was stirred overnight. 60 cm³ of water were added to thedark-red solution, and the solution, which had become yellow, wasextracted with ether. The ether phase was dried over MgSO₄, concentratedand left to crystallize at -35° C. 5.1 g (42%) of1,1-cyclopentadienyl-(9-fluoroenyl)diphenylmethane were obtained as abeige powder.

2.0 g (5.0 mmol) of the compound were dissolved in 20 cm³ of THF, and6.4 cm³ (10 mmol) of a 1.6 molar solution of butyllithium in hexane wereadded at 0° C. The mixture was stirred at room temperature for 15minutes, the solvent was stripped off, and the red residue was dried inan oil-pump vacuum and washed several times with hexane. After havingbeen dried in an oil-pump vacuum, the red powder was added at -78° C. toa suspension of 1.16 g (5.00 mmol) of ZrCl₄. The batch was slowly warmedand then stirred at room temperature for a further 2 hours. The pinksuspension was filtered through a G3 frit. The pink residue was washedwith 20 cm³ of CH₂ Cl₂, dried in an oil-pump vacuum and extracted with120 cm³ of toluene. The solvent was stripped off and the residue driedin an oil-pump vacuum to give 0.55 g of the zirconium complex in theform of a pink crystal powder.

The orange filtrate from the reaction batch was concentrated and left tocrystallize at -35° C. A further 0.45 g of the complex crystallized fromCH₂ Cl₂.

Overall yield 1.0 g (36%). Correct elemental analysis. The mass spectrumshowed M⁺ =556. ¹ H-NMR spectrum (100 MHz, CDCl₃): 6.90-8.25 (m, 16,Flu-H, Ph-H), 6.40 (m, 2, Ph-H), 6.37 (t, 2, Cp-H), 5.80 (t, 2, Cp-H).

B) Preparation of COC I

A clean and dry 75 dm³ polymerization reactor fitted with a stirrer wasflushed with nitrogen and then with ethylene and filled with 22,000 g ofnorbornene melt (Nb). The reactor was then heated to a temperature of70° C. with stirring, and 10 bar of ethylene were injected.

580 cm³ of a toluene solution of methylaluminoxane (10.1% by weight ofmethylaluminoxane having a molecular weight of 1300 g/mol, determinedcryoscopically) were then metered into the reactor, and the mixture wasstirred at 70° C. for 15 minutes, during which the ethylene pressure waskept at 10 bar by subsequent metering-in. In parallel, 500 mg ofdiphenylmethylene(9-fluoroenyl)cyclopentadienylzirconium dichloride weredissolved in 1000 cm³ of a toluene solution of methylaluminoxane(concentration and quality, see above) and preactivated by standing for15 minutes. The solution of the complex (catalyst solution) was thenmetered into the reactor (in order to reduce the molecular weight,hydrogen can be introduced into the reactor via a transfer channelimmediately after the catalyst had been metered in). The mixture wasthen polymerized at 70° C. for 140 minutes with stirring (750 rpm), theethylene pressure being kept at 10 bar by subsequent metering-in. Thereactor contents were then rapidly discharged into a stirred vesselcontaining 200 cm³ of isopropanol (as stopper). The mixture wasprecipitated in acetone and stirred for 10 minutes, and the suspendedpolymeric solid was then filtered off.

A mixture of two parts of 3N hydrochloric acid and one part of ethanolwas then added to the filtered-off polymer and the mixture was stirredfor 2 hours. The polymer was then filtered off again, washed with wateruntil neutral and dried at 80° C. and 0.2 bar for 15 hours. 4400 g ofproduct were obtained. A viscosity of 142 cm³ /g and a glass transitiontemperature (T_(g)) of 168° C. were measured on the product.

Cycloolefin copolymer II [COC II]

A) Preparation of rac-dimethylsilylbis(1-indenyl)-zirconium dichloride

All the work operations below were carried out in an inert-gasatmosphere using absolute solvents (Schlenk Technik).

A solution of 30 g (0.23 mol) of indene (technical grade, 91%), filteredthrough aluminum oxide, in 200 cm³ of diethyl ether was treated, withice cooling, with 80 cm³ (0.20 mol) of a 2.5 molar solution ofn-butyllithium in hexane. The batch was stirred at room temperature fora further 15 minutes, and the orange solution was added via a cannulaover the course of 2 hours to a solution of 13.0 g (0.10 mol) ofdimethyldichlorosilane (99%) in 30 cm³ of diethyl ether. The orangesuspension was stirred overnight and extracted three times by shakingwith 100-150 cm³ of water. The yellow organic phase was dried twice oversodium sulfate and evaporated in a rotary evaporator. The orange oilwhich remained was kept at 40° C. for 4 to 5 hours in an oil-pump vacuumand freed from excesss indene, a white precipitate being formed. Byadding 40 cm³ of methanol and crystallizing the product at -35° C., atotal of 20.4 g (71%) of the compound (CH₃)₂ Si(Ind)₂ were isolated as awhite to beige powder. M.p. 79°-81° C. (2 diastereomers).

A solution of 5.6 g (19.4 mmol) of (CH₃)₂ Si(Ind)₂ in 40 cm³ of THF wastreated slowly at room temperature with 15.5 cm³ (38.7 mmol) of a 2.5molar hexane solution of butyllithium. After 1 hour from completion ofthe addition, the dark-red solution was added dropwise over the courseof 4-6 hours to a suspension of 7.3 g (19.4 mmol) of ZrCl₄ ·2THF in 60cm³ of THF. The mixture was stirred for 2 hours, and the orangeprecipitate was filtered off with suction through a glass frit andrecrystallized from CH₂ Cl₂. 1.0 g (11%) of a rac-(CH₃)₂ Si(Ind)₂ ZrCl₂was obtained in the form of orange crystals, which gradually decomposefrom 200° C.

Correct elemental analysis. The EI mass spectrum showed M⁺ =448. ¹ H-NMRspectrum (CDCl₃): 7.04-7.60 (m, 8, arom. H), 6.90 (dd, 2, β-Ind H), 6.08(d, 2, α-Ind H), 1.12 (s, 6, SiCH₃).

B) Preparation of COC II

A clean and dry 1.5 dm³ polymerization reactor fitted with stirrer wasflushed with nitrogen and then with ethylene and filled with a solutionof 180 g of norbornene in 750 cm³ of toluene. The reactor was thenheated to a temperature of 20° C. with stirring, and 1 bar of ethylenewas injected.

20 cm³ of a toluene solution of methylaluminoxane (10.1% by weight ofmethylaluminoxane having a molecular weight of 1300 g/mol, determinedcryoscopically) were then metered into the reactor, and the mixture wasstirred at 20° C. for 15 minutes, the ethylene pressure being kept at 1bar by subsequent metering-in (saturation of the toluene with ethylene).In parallel, 60 mg of rac-dimethylsilyl-bis(1-indenyl)zirconiumdichloride were dissolved in 10 cm³ of a toluene solution ofmethylaluminoxane (concentration and quality, see above) andpreactivated by standing for 15 minutes. The solution of the complex wasthen metered into the reactor. The mixture was then polymerized at 20°C. for 3 hours with stirring (750 rpm), the ethylene pressure being keptat 10 bar by subsequent metering-in. The reactor contents were thenrapidly discharged into a stirred vessel containing 100 cm³ ofisopropanol. 2 dm³ of acetone were added and the mixture was stirred for10 minutes, and the suspended polymeric solid was then filtered off.

The filtered-off polymer was then introduced into 300 cm³ of a mixtureof two parts of 3N hydrochloric acid and one part of ethanol, and thissuspension was stirred for 2 hours. The polymer was then filtered offagain, washed with water until neutral and dried at 80° C. and 0.2 barfor 15 hours. 54.1 g of product were obtained. A viscosity of 177 cm³ /gand a glass transition temperature (T_(g)) of 145° C. were measured onthe product.

The polymers listed were first dried (130° C., 24 hours, vacuum) andsubsequently jointly extruded, in various ratios by weight, in ameasuring extruder (HAAKE, Rheocord System 90/Rheomex 600, Karlsruhe,Germany) under an inert gas (argon) and granulated. The resultantgranules were dried (130° C., 24 hours, vacuum) and subsequently used tomeasure the flow properties (melt flow index tester MPS-D fromGoettfert, Buchen, Germany, and capillary viscometer) or dried in anevacuable press (130° C., 24 hours, vacuum) and subsequently pressed toform sheets (340° C., 10 bar, 5 minutes) in order to measure thewater-absorption capacity (storage time: 13 days at 23° C. and arelative atmospheric humidity of 85%). The Staudinger indices weredetermined as described in "Praktikum der makromolekularen Chemie"[Practical Macromolecular Chemistry] by Braun, Cherdron and Kern, HuttigVerlag, Heidelberg.

The melt flow index was determined in accordance with DIN 53735-MFI-B(plunger load 5 kp, 340° C., cylinder: internal dimensions 9.55±0.01 mm,length at least 115 mm, exit nozzle 2.095±0.005 mm). The viscositieswere determined in accordance with DIN 53728 (solvent:decahydronaphthalene, 135° C., concentration: 0.001 g/cm³).

EXAMPLE A

PEA I was extruded together with COC I in various weight ratios by meansof a twin-screw extruder (all four zones at 340° C.), and the extrudatewas granulated. The granules were subsequently dried for 24 hours at130° C. in vacuo and used to measure the flow properties and thewater-absorption capacity of the alloys. Table 1 shows the dataobtained.

                  TABLE 1                                                         ______________________________________                                        Physical properties of the PEA I/COC I alloy                                  PEA I   COC I                Water-absorption                                 [% by   [% by      MFI       capacity                                         weight] weight]    [g/10 min]                                                                              [% by weight]                                    ______________________________________                                        100      0          6        2.30                                              90      10        11        1.40                                              0      100        55        0.05                                             ______________________________________                                    

The results show that the alloys of the invention have a lower meltviscosity and water-absorption capacity than do the polyether-amidesalone.

EXAMPLE B

PEA II was extruded together with COC II in various weight ratios bymeans of a twin-screw extruder (all four zones at 340° C.), and theextrudate was granulated. The granules were subsequently dried for 24hours at 130° C. in vacuo and used to measure the flow properties andthe water-absorption capacity of the alloys. Table 2 shows the dataobtained.

                  TABLE 2                                                         ______________________________________                                        Physical properties of the PEA II/COC II alloy                                PEA I   COC I                Water-absorption                                 [% by   [% by      MFI       capacity                                         weight] weight]    [g/10 min]                                                                              [% by weight]                                    ______________________________________                                        100      0          7        2.50                                              90      10        11        1.20                                              0      100        48        0.05                                             ______________________________________                                    

The results show that the alloys of the invention have a lower meltviscosity and water-absorption capacity than do the polyether-amidesalone.

The examples below relate to the preparation of polyether-amides (a).

EXAMPLES

The Staudinger index [η]_(o) was determined in N-methylpyrrolidone at25° C. The following abbreviations were used for the examples below:

BAS=2,2-bis[4-(4-aminophenoxy)phenyl]-propane

TPC=terephthaloyl chloride

IFC=isophthaloyl chloride

FDC=2,5-furandicarbonyl chloride

FBC=4-fluorobenzoyl chloride

BCl=benzoyl chloride

NMP=N-methylpyrrolidone

CaO=calcium oxide

E-mod.=modulus of elasticity

MFI=melt flow index

DSC=differential scanning calorimetry

M_(W) =weight average molecular weight

M_(n) =number average molecular weight

D=M_(w) /M_(n) =polydispersity, nonuniformity, molecular weightdistribution

TGA=thermogravimetric analysis

T_(g) =glass transition temperature (determined as the inflection pointof the glass state in the DCS)

PS=polystyrene, M(PS)=apparent molecular weight determined in the GPCrelative to polystyrene

PO=1,2-propylene oxide

BAPS=bis[4-(4-aminophenoxy)phenyl]sulfone

GPC=gel permeation chromatography

PA=phthalic anhydride

Demin. water=demineralized water

UL 94=Underwriters Laboratories (USA) Bulletin 94 (test standard forflammability)

MH=Mark/Houwink equation: [η]_(o) =k·M_(w) ^(a)

[η]_(o) =Staudinger index, unit dl/g

η_(m) =melt viscosity, unit Pa.s

DMF=dimethylformamide

DMAC=N,N-dimethylacetamide

EXAMPLE 1

Polyether-amide made from 2,2-bis [4-(4-aminophenoxy)-phenyl]propane,terephthalic acid and benzoyl chloride in N-methylpyrrolidone:

4105 g (10 mol) of BAB were dissolved in 15.24 l of NMP under nitrogenin an enameled 40 l stirred reactor with heating jacket. After thetemperature had equilibrated at 25° C., 1959 g (9.65 mol=96.5%) of TPC,dissolved in 5 l of NMP, were added. 30 minutes after the mixture hadreached 70° C., 112.5 g (0.8 mol) of BCl were added, after a further 30minutes the mixture was cooled to 60° C., and 566 g (10.1 mol) of CaO asa suspension in 305 g of NMP were added. After 1 hour, the clear,viscous solution was discharged from the reactor, diluted from a polymercontent of 20% to about 13% by means of about 13 l of NMP, and filteredunder an N₂ pressure of 3 bar, and finally the polymer was precipitatedas a fine powder (particle size≦1 mm) using water. The polymer powderwas washed four times for 2 hours in each case with 60 l of fresh,demin. water at 95°-98° C. in a stirred pressure filter, dried roughlyin a hot stream of nitrogen and washed a further twice with 60 l ofacetone (2 hours, 60° C.). The product was predried overnight in astream of nitrogen, subsequently dried for 14 hours at 130° C. (100mbar) and finally dried to completion for 8 hours at 150° C. (<10 mbar).Yield 5.0 kg (93%). [η]_(o) =1.06 dl/g; M_(w) =40,000 g·mol⁻¹ ; ashcontent: 200 ppm; GPC: M_(n) (PS)=50,000, D=2.1.

EXAMPLES 2-7

In an analagous manner as in Example 1, 4105 g (10 mol) of BAB werereacted with 1949 g (9.6 mol=96%) of TPC or isophthaloyl chloride and126.5 g (0.9 mol) of BCl in 20.8 kg of NMP:

    ______________________________________                                                   Staudinger                                                                              M.sub.n (PS)                                             Ratio      index     from      M.sub.w                                        Ex.  TPC/IPC   [η].sub.o /dl/g                                                                     GPC   D   from MH                                                                              T.sub.g.sup.b) /°C.          ______________________________________                                        2    1/0       0.86      39,000                                                                              2.1 36,000 227                                 3    8/2       0.69      34,000                                                                              2.2 26,000 221                                 4    7/3       0.68      32,000                                                                              2.2 25,000 224                                 5    6/4       0.68      36,000                                                                              2.1 25,000 222                                 6    5/5       0.68      35,000                                                                              2.0 25,000 226                                 7.sup.a)                                                                           7/3       0.80      44,000                                                                              2.0 32,000 227                                 ______________________________________                                         .sup.a) Example 7 as for Example 4, but TPC/BAB = 965/1000 (molar ratio)      .sup.b) Polymers 3-7 are Xray amorphous.                                 

EXAMPLE 8

Polyether-amide made from BAB, TPC, 4-fluorobenzoyl chloride and1,2-propylene oxide in NMP:

246.3 g (0.6 mol) of BAB were dissolved in 1615 g of dry NMP undernitrogen. 118.16 g (0.582 mol=97%) of TPC were added at 10° C. Themixture was warmed to 50° C. (about 0.5 hour), and 5.7 g (36 mmol=6%) ofFBC were added. After 40 minutes, a mixture of 73.2 g (1.26 mol) of POand 88 g of NMP was added dropwise via a dropping funnel. The mixturewas filtered, and the product was precipitated in demineralized waterand washed several times with hot demin. water and subsequently a numberof times with acetone. The product was predried at about 100 mbar andfinally dried for 8 hours at 150° C. and 10 mbar. Ash content: 460 ppm.

EXAMPLE 9

287.4 g (0.7 mol) of BAB were dissolved in 1708 g of dry NMP undernitrogen. 139.27 g (0.686 mol=98%) of TPC were added at 3° C. Themixture was warmed to 50° C., and 5.6 g (35 mmol=5%) of FBC were added.After 1 hour, a mixture of 85.4 g (1.47 mol) of PO and 88 g of NMP wasadded dropwise via a dropping funnel. Work-up was as in Example 8. Ashcontent: 350 ppm.

EXAMPLE 10

Polyether-amide made from BAB, TPC, isophthaloyl chloride, FBC and PO inNMP:

410.5 g (1.0 mol) of BAB were dissolved in 1816 g of dry NMP undernitrogen. A homogeneous mixture of 99.48 g of each of TPC and IPC (ineach case 0.49 mol, together 0.98 mol=98%) was added at 5° C. andsubsequently rinsed with 100 ml of NMP. When an internal temperature of50° C. had been reached (about 0.5 hour), 6.34 g (40 mmol=4%) of FBCwere added. After 1 hour, a mixture of 122 g (2.1 mol) of PO and 147 gof NMP was added dropwise. Work-up was as in Example 8. Ash content: 100ppm.

                  TABLE                                                           ______________________________________                                        Examples 8-10                                                                      Molar                         Fluorine                                                                             Ash                                      ratio                   % F   content                                                                              content/                            Ex.  %       [η].sub.a.sup.a)                                                                 % F (NMR).sup.b)                                                                       (EA).sup.c)                                                                         calc./%.sup.d)                                                                       ppm                                 ______________________________________                                        8    97      1.10   0.195 + 0.010                                                                          0.18  0.21   460                                 9    98      1.40   0.157 + 0.008                                                                          0.14  0.14   350                                 10   98      1.35   0.135 + 0.007                                                                          0.11  0.14                                       ______________________________________                                         .sup.a) Staudinger index in dl/g                                              .sup.b) Measured as the 4fluorobenzamide terminal group in the .sup.19        FNMR spectrum                                                                 .sup.c) Elemental analysis (EA)                                               ##STR7##                                                                      ##STR8##                                                                 

In polymers 8-10 according to the invention, 79-100% of the fluorinefrom the 4-fluorobenzamide terminal groups was recovered.

EXAMPLES 11, 12 and 13

This series of experiments shows that an excess of chain terminator(here BCl) does not adversely affect the fusible polymer.

    ______________________________________                                        Ex.      %.sup.a)                                                                             [η].sub.o /dl/g                                                                       M.sub.n (PS)/gmol.sup.-1                                                                 D                                      ______________________________________                                        11       8      0.95 ± 0.04                                                                            62,000     1.81                                   12       9      0.96 ± 0.04                                                                            63,000     1.82                                   13       10     1.03 ± 0.05                                                                            61,000     1.83                                   Mean     /      0.98        62,000     1.82                                   ______________________________________                                         .sup.a) Mole percent of chain terminator benzoyl chloride (BCl); 7 =          stoichiometric                                                           

The experiments showed--within expermiental accuracy--no differencebetween the polymers 11, 12 and 13. The samples also behaved in acomparable manner in a measuring compounder at 340° C.

EXAMPLE 11

410.5 g (1.0 mol=100%) of BAB were introduced into 2009 g of dry NMP at3° C. under nitrogen, and 195.91 g (0,965 mol=96.5%) of TPC were added.The mixture was warmed first to 50° C. and subsequently to 70° C. (about0.5 h). 11.24 g (0.08 mol=8%) of BCl were added, the mixture was stirredat 70° C. for a further 30 minutes, and finally a liquid mixture of 128g of PO and 154 g of NMP was added dropwise. Work-up was as in Example8. Ash content: 98 ppm.

EXAMPLE 12

Procedure as for Example 11, but 9%=0.09 mol=12.65 g of BCl were addedinstead of 8%.

EXAMPLE 13

Procedure as for Example 11, but 10%=0.1 mol=14.57 g of BCl were addedinstead of 8%. Ash content: 59 ppm

EXAMPLE 14

Polyether sulfone amide made from bis[4-(4-aminophenoxy)phenyl]sulfone,TPC, IPC and BCl in NMP:

As in Example 1, but with the following starting materials:

3676 g (8.5 mol) of BAPS (purity 98.6%)

828.3 g (4.08 mol) each of IPC and TPC (8.16 mol=96%)

106.8 g (0.76 mol=9%) of BCl and

518 g (9.24 mol) of CaO in a total of 18,270 g of NMP.

Instead of acetone, which acts as a plasticizer, methanol was used forrinsing.

Staudinger index: [η]_(o) =0.81 dl/g GPC: M_(n) (PS)=56,000 g/mol;D=M_(w) /M_(n) =2.2

EXAMPLE 15

Phthalic anhydride as chain terminator

Polyether-amide made from BAB, TPC, phthalic anhydride and PO in NMP:

410.5 g (1.0 mol=100%) of BAB were introduced into 2020 g of dry NMP at3° C. under nitrogen, and 106.93 g (0.97 mol=97%) of TPC were added. Themixture was subsequently heated to 50° C. while stirring was continued,and 8.89 g (0.06 mol=6%) of PSA were added. After 1 hour, a mixture of118 g of PO and 143 g of NMP was added dropwise. The mixture was workedup as described in Example 8 and additionally dried at 200° C. (3hours), giving 505 g (93%) of a colorless polymer powder which had thefollowing properties:

Staudinger index: [η]_(o) -1.1 dl/g GPC: M_(n) (PS)=66,000 g/mol,D=M_(w) /M_(n) =2.4.

The 300 MHz ¹ H-NMR spectrum and the corresponding ¹³ C-NMR spectrum(solvent DMSO-d₆) showed the following signals, which are characteristicof the phthalimido terminal group:

7.86-7.96 ppm (m, 2 mol %), and 124, 132, 135 and 167 ppm. Within thelimits of measurement accuracy, all the terminal groups are in the formof the phthalimide. The compounding experiment at 340° C. showed nodestruction of the melt after 30 minutes.

EXAMPLE 16

Polyether-amide using NH₃ gas as neutralizer

Example 11 was repeated, with the difference that NH₃ gas was passedinto the solution after 30 minutes from addition of the BCl, and, aftera further 30 minutes, 50 ml of glacial acetic acid were added to bufferthe excess of NH₃. The precipitated NH₄ Cl was filtered off, and theproduct was worked up as described above in Example 8.

Staudinger index: [η]_(o) =0.96 dl/g GPC:M_(n) (GPC)=53,000 g/mol, D=2.1Ash content: 156 ppm.

EXAMPLE 17

Polyether-amide using water as HCl binder

Example 11 was repeated, but no neutralizer was added; instead, thehydrochloric acid solution of the polymer was added dropwise from aglass dropping funnel directly into demin. water. The water thus servednot only to precipitate the polymer, but also to bind the formed HCl asaqueous, dilute hydrochloric acid. After work-up as in Example 8, an ashcontent of 30 ppm was determined.

EXAMPLE 18

Copolymer with a second diamine

Example 8 was repeated, but 20 mol % of the BAB were replaced by4,4'-diamino-3,3'-dimethylbiphenyl, and the FBC was replaced by BCl. Thepolymer worked up and dried as in Example 8 had a glass transitiontemperature (DSC) of 228° C. Staudinger index: [η]_(o) =1.09 dl/g,corresponding to M_(w) =51,000 g/mol. GPC: M_(n) =66,000 g/mol; D=2.1.

EXAMPLES 19-24

Amides were prepared in corresponding manner to the above examples fromBAB and 2,5-furandicarbonyl dichloride as one of the acid components.

    ______________________________________                                              %      %       %    Molar ratio                                         Ex.   FDC    IPC     TPC  %       BCl/% Neutralizer                           ______________________________________                                        19     50    --      50   97      6     PO                                    20    100    --      --   94.5    12    CaO                                   21     50    --      50   97      8.8   CaO                                   22    100    --      --   97      6     CaO                                   23    100    --      --   95      10    CaO                                   24     20    20      60   96.5    8     CaO                                   ______________________________________                                    

EXAMPLE 25

Polyether-amide made from 2,6-naphthalenedicarbonyl dichloride (NDC) andBAB

410.5 g (1.0 mol) of BAB were dissolved in 2051 g of dry NMP undernitrogen. 244.3 g (0.965 mol) of NDC were added at 5° C. The internaltemperature first increased to 35° C.; the mixture was subsequentlywarmed to 70° C. After 60 minutes, 11.8 g (0.084 mol) of BCl were added,and, after a further 30 minutes, 62 g (1.1 mol) of CaO as a suspensionin 33 g of NMP were added. The mixture was stirred for a further 90minutes and worked up as in Example 8.

The investigation results are summarized in the table below.

EXAMPLES 26-30

Copolyether-amides made from NDC and other diacid chlorides

Analogous to Example 25, but BAB was introduced into 1200 g of NMP, andthe homogeneous solution was added to the acid chlorides indicated inthe table below in 763 g of NMP.

    __________________________________________________________________________    %     %  %  %          GPC analysis                                                                            DSC                                          Ex.                                                                              NDC                                                                              TPC                                                                              IPC                                                                              FDC                                                                              [η].sub.o /dl · g.sup.-1                                                 M.sub.n (PS standard)D                                                                  T.sub.g.sup.a)                                                                   T.sub.g.sup.b)                            __________________________________________________________________________    25 100                                                                              0  0  0  1.13 ± 0.01                                                                        43,000                                                                             2.9  229                                                                              228.sup.c)                                26 50 50 0  0  0.83 ± 0.01                                                                        35,000                                                                             2.4  226                                                                              225                                       27 50 0  50 0  0.85 ± 0.05                                                                        31,000                                                                             2.7  226                                                                              226.sup.d)                                28 70 0  30 0  0.89 ± 0.01                                                                        42,000                                                                             2.3  228                                                                              228                                       29 70 0  0  30 0.80 ± 0.03                                                                        41,000                                                                             2.3  227                                                                              228                                       30  331/3                                                                           0  331/3                                                                            331/3                                                                            0.83 ± 0.05                                                                        38,000                                                                             2.2  223                                                                              227                                       __________________________________________________________________________     .sup.a) Glass transition temperature of the polymer powder                    .sup.b) Glass transition temperature of the pressed plate (vacuum,            340° C., 15 minutes: 0 bar; 5': 100 bar)                               .sup.c) Additionally a weak melt peak at 350°  C. (1.1 J/g)            .sup.d) Additionally a weak melt peak at 335° C. (0.5 J/g)        

EXAMPLE 31

Copolyether-amide made from TPC, BAB and 2,2-bis(4-aminophenyl)propane(PBA)

Analagous to Example 25, but 246.3 g (0.6 mol) of BAB and 135.6 g (0.6mol) of PBA were introduced into 2030 g of NMP and polycondensed with235.1 g (1.158mol=96.5%) of TPC. Finally, 14.2 g (0.11 mol) of BCl and74 g (1.3 mol) of CaO, suspended in 40 g of NMP, were added. Afterwork-up as in Example 8, the following were measured:

Staudinger index [η]_(o) =0.82±0.01 dl/g GPC (PS): M_(n) =35,000 g/mol;D=2.2.

We claim:
 1. A polymer alloy containing at least two components (a) and(b), wherein(a) is at least one thermoplastic aromatic polyether-amideof the formula (I) ##STR9## in which the symbols --Ar--, --Ar'--, --Ar₁--, --Ar₂ --, --R--, --R'--, --Y--, x, y and z are as definedbelow:--Ar-- is at least one divalent, aromatic radical orheteroaromatic radical or an --Ar*--Q--Ar*-- group where --Ar*-- is adivalent aromatic radical, --Q' is a bond or an --O--, --CO--, --S--,--SO-- or --SO₂ -- bridge, --Ar'-- is as defined for --Ar-- or is an--Ar--C(CH₃)₂ --Ar-- or --Ar--O--Ar*--O--Ar-- where --Ar*-- is adivalent aromatic radical, --Ar₁ -- and --Ar₂ -- are identical ordifferent and are each a para- or meta- arylene radical, --Y-- is a--C(CH₃)₂ --, --SO₂ --, --S-- or --C(CF₃)₂ -- bridge, where the sum ofthe molar fractions x, y and z is one, the sum of x and z is not equalto y, and only x can adopt the value zero, the ends of the polymer chainare fully blocked by monofunctional groups --R and --R' which areselected from the group consisting of benzoyl, anilino, phthaloylimidoand naphthalimido radicals, which radicals may be substituted by ahalogen atom or an organic residue and the polyether-amide has aStaudinger index of from 0.4 to 1.5, measured at 25° C. inN-methyl-2-pyrrolidone and (b) is at least one cycloolefin polymer,where the proportion of (a) is 99-50% by weight, and the proportion of(b) is 1-50% by weight, based on the sum of the proportions of (a) and(b).
 2. The polymer alloy as claimed in claim 1, wherein the proportionof component (a) is 98-60% by weight and that of component (b) is 2-40%by weight.
 3. The polymer alloy as claimed in claim 2, wherein theproportion of component (a) is 95-85% by weight and that of component(b) is 5-15% by weight.
 4. The polymer alloy as claimed in claim 1,wherein the viscosity of component (b) is greater than 20 cm³ /g.
 5. Thepolymer alloy as claimed in claim 1, wherein the structural element##STR10## of component (a) is derived from 2,5-furandicarboxylic acid,terephthalic acid or isophthalic acid, or a combination thereof.
 6. Thepolymer alloy as claimed in claim 1, wherein component (a) containsstructural units derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propaneor bis[4-(4'-aminophenoxy)phenyl]sulfone, or a combination thereof. 7.The polymer alloy as claimed in claim 1, wherein component (b) containsstructural units derived from at least one monomer of the formulae IX toXIV or XV ##STR11## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ areidentical or different and are hydrogen atoms or C₁ -C₈ -alkyl radicals,andn is an integer from 2 to
 10. 8. The polymer alloy as claimed inclaim 7, wherein, in addition to the structural units derived from atleast one monomer of the formulae IX to XV, component (b) containsfurther structural units derived from at least one acyclic 1-olefin ofthe formula XVI ##STR12## in which R⁹, R¹⁰, R¹¹ and R¹² are identical ordifferent and are hydrogen atoms or C₁ -C₈ -alkyl radicals.
 9. Thepolymer alloy as claimed in claim 8, wherein component (b) is acopolymer of polycyclic olefins of the formula IX or XI and at least oneacyclic olefin of the formula XVI.
 10. The polymer alloy as claimed inclaim 1, wherein component (a) contains structural units of thefollowing formula ##STR13## and component (b) is a copolymer ofnorbornene and ethylene.
 11. The polymer alloy as claimed in claim 1,wherein component (a) contains structural units of the followingformulae ##STR14## and component (b) is a copolymer of norbornene andethylene.
 12. A polymer alloy molding comprising the polymer alloy asclaimed in claim
 1. 13. The polymer alloy as claimed in claim 1, whereinthe radical --Ar-- of the polyether-amide (a) carries one or twosubstituents selected from C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, aryl, aryloxy,branched or unbranched C₁ -C₆ -perfluoroalkyl and perfluoroalkoxyradicals, fluorine, chlorine, bromine and iodine.
 14. The polymer alloyas claimed in claim 1, wherein 2 or 3 different radicals Ar are bondedsimultaneously in the polyether-amide (a).